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The recently reported syntheses and X‐ray crystal structures of the highly endothermic compounds F6XeNCCH3 and F6Xe(NCCH3)2⋅CH3CN provide the first, albeit weakly covalent, XeVI−N bonds. The XeF6 unit of F6XeNCCH3 possesses distorted octahedral (C3v) symmetry similar to gas‐phase XeF6, whereas the XeF6 unit of F6Xe(NCCH3)2⋅CH3CN possesses C2v symmetry. Herein, the natural bond orbital (NBO), atoms...
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